Mixed sulfite esters of acyclic alkynyl alcohols and alkanols or phenols



.chlorophenyl, trichlorophenyl, pentachlorophenyl.

the yield of chlorosulfinate is nearly quantitative.

United States Patent MTXED SULFITE ESTERS OF ACYCLIC ALKYNYL This application is a continuationein-part of our application Serial No. 131,742, filed August 16, 1961, and now abandoned.

This invention relates to new chemicals, namely, new organic esters of sulfurous acid, more particularly to mixed sulfite esters of acyclic alkynyl alcohols and saturated aliphatic alcohols or phenols.

The new compounds of the present invention are useful as insecticides, particularly for the control of insects and mites. They may also be used as plasticizers.

The chemicals of the present invention may be represented by the general formula RO-S -O-R' in which R is an aliphatic radical, e.g. alkyl having up to 18 carbon atoms, aralkyl, cyanoalkyl, haloalkyl having up to carbon atoms and up to 3 halo radicals or carbalkoxyalkyl radical, or R is an aromatic radical, e.g. aryl (phenyl or naphthyl), alkaryl or haloaryl, and R is an acyclic alkynyl radical. Examples of R are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, amyl, heXyl, 2-ethylhexyl, octyl, decyl, isodecyl, dodecyl,

hexadecyl, octadecyl, benzyl, 2-chloroethyl, 2-cyanoethy1,

2-carbethoxyethyl, 2,2,2-trichloroethyl, 'y-chloropropyl, 6- chlorobutyl, w-trichloroamyl, phenyl, l-naphthyl, 2-naphthyl, p-tolyl, o-tolyl, isopropylphenyl, tert.-butylphenyl, tert.-amyl phenyl, nonylphenyl, and haloaryl having 1 to 5 halo radicals, e.g. bromophenyl, 2-chl0rophenyl, 2,4-di- Examples of R are acyclic alkynyl radicals having 3 to carbon atoms, i.e. C H radicals Where n is 3 to 10, e.g. propargyl, I-(Z-butynyl), 2-(3-butynyl), 2-(2-methyl- 3-butynyl) 1- (2-heptynyl 1-(3-nonynyl).

The preparation of the chemicals of the invention may be carried out by reacting the selected alkynyl alcohol with the separately prepared chlorosulfinate of the selected alcohol or phenol, which may be made by reacting the selected aliphatic or aromatic monohydroxy compound (alcohol or phenol) with thionyl chloride. Such preparation is illustrated by the following reactions with the same symbols R, R as in the above general formula.

I non+s0o1 n-o so1+:ao1

i i R-OSC1+ HOR R-OSOR HCl The first reaction is carried out at a temperature of between 5 C. and 30 C., preferably near 0 C., and An inert solvent such as benzene, xylene or solvent naphtha may be used, but is generally unnecessary. The second reaction is carried out in the presence of an HCl acceptor, such as pyridine, dimethyl aniline or trimethylamine, and in a solvent such as benzene, xylene or solvent naphtha.

The reaction temperature is generally between 10 C. r

tion are: Propargyl hexyl sulfite Propargyl sec.-octyl sulfite C 3,179,684 lcg Patented Apr. 21), 1965 t 2 Propargyl is'odecyl sulfite Propargyl tridecyl sulfite Propargyl hexadecyl sulfite Propargyl benzyl sulfite Propargyl 2-chloroethyl sulfite Propargyl Z-cyanoethyl sulfite Propargyl 2-carbethoxyethyl sulfite Propargyl phenyl sulfite Propargyl o-tolyl sulfite Propargyl p-tert.-butylphenyl sulfite. Propargyl l-naphthyl sulfite Propargyl nonylphenyl sulfite Propargyl o-chlorophenyl sulfite 2- 3-butynyl decyl sulfite 2-(3-butyny1) hexadecyl sulfite 2-(3-butynyl) m-tolyl sulfite I-(Z-butynyl) dodecyl sulfite 1-(2-butynyl) p-tert.-amylphenyl sulfite 1-(3-hexynyl) octadecyl sulfite 1-(3-hexyny1) o-tert.-butylpheny1 sulfite Example I illustrates the preparation of the compounds of the present invention.

EXAMPLE I Preparation of propargyl tridecyl sulfite Tridecyl alcohol (100 g., 0.5 mole) was cooled to 05 C. Thionyl chloride (45.4 ml., 74.4 g., 0.625 mole) was added during one hour keeping the reaction temperature below 10 C. The mixture was allowed to warm to room temperature and stand for 15 hours. The mixture was warmed to 50 C. (0.5 mm.) to remove unreacted thionyl chloride. The tridecyl chlorosulfinate residue was an amber-colored oil, yield 141.0 g. (99.8%). The

7 due distilled, B.P. 122-136. C. (0.1 mm.).

product was nearly odorless and relatively stable when stored in a refrigerator.

Propargyl alcohol (3.2. ml., 3.1 g., 0.055 mole) 4.1 ml. (4.0 g., 0.05 mole) pyridine and 60 ml. xylene were combined and the solution cooled to 0-5" C. Tridecyl chlorosulfinate (14.2 g., 0.05 mole) was added dropwise during 0.5 hr. maintaining the reaction temperature below 8 C. The mixture was stirred for one hour and was washed twice with 25 ml. portions of watch The mixture was then stirred for 1.5 hrs. with 2 N NaOH. The xylene solution was washed several times with saturated salt solution until the washings were neutral to pH paper. The Xylene was removed under reduced pressure and the resi- Yield 11.4 g. (71%) colorless oil, 11 1.4596. Analysis.Calculated for C H O S: C, 63.53%; H, 10.00%; S, 10.60%. Found: C, 64.27%, 64.13%; H, 10.08%, 10.05%; S, 10.39%, 9.34%.

Sulfur analyses of other chemicals of the present invention were:

2-(3-butynyl) hexadecyl sulfite. Calculated S: 8.94%. Found: 8.34%.

Propargyl decyl sulfite. Calculated S: Found: 12.22%.

I-(Z-butynyl) tridecyl sulfite. Found: 10.14%.

Propargyl o-tolyl. sulfite. Found: 15.25%.

Propargyl hexadecyl sulfite. Calculated S: 9.31%. Found; 8.63%.

Calculated S: 10.13%.

Calculated S: 15.26%.

EXAMPLE II p This example illustrates the insecticidal activity of the chemicals of the present invention in tests against the larvae of Aedes aegypti (L.) mosquitoes. Fourth instar larvae were used. These larvae normally reach this stage in 5 days at F. after hatching.

To 10 mg. of the chemicalto be tested was added 1 ml. of acetone and ml. of water to give a concentration of '100 parts per million (p.p.m.), and a portion was also diluted to '10 ppm.

Twenty-five ml. aliquots, replicated once, of the chemical to be tested at concentrations of 100 ppm. and 10 ppm. and of checks without the chemical and of plain water checks were placed in test tubes and from to 25 larvae were added. The tubes were held at 70 F. in darkness for 72 hours. At the end of this period the live and dead larvae werecounted and the percent mortality calculated. All the larvae were alive in the checks (0% mortality). Thepercent mortality of the larvae treated with the chemical of the present invention is shown in the following table:

EXAMPLE III This example illustrates the effectiveness of the chemicals of the present invention for controlling mites.

Pinto beans in the two-leaf state and grown in 4" baskets under greenhouse conditions at 70 F.-75 F. were used. Three plants for a total of six leaves were in "each basket for each test. The tests on the chemicals and checks were replicated once. Aqueous suspensions of the chemicals were prepared by adding to 0.2 gram of the chemical one drop (0.03 gram) of a commercial surfaceactive dispersing agent (isooctylphenyl polyethoxy ethanol) and lrnl. of acetone, washing into 200 ml. of water, agitating to form a dispersion and diluting with water to the desired concentrations of 1000 ppm. and 200 ppm. The-plants were sprayed with the dispersions of the chemicals at the various concentrations and the check plants were sprayed with aqueous solutions containing surface-active agent and acetone without the chemicals. The sprayings thoroughly wet theupper surface of the leaves. The plants were returned to the-greenhouse. The followingday (20-24 hours later), rings of an adhesive preparation non-toxic to the organisms under test, such .as is used on fly papers and for ringing trees, were placed around the borders of the upper surfaces of the leaves to restrict the mites to the upper leaf surface. Mites were transferred to the thus treated leaves by placing bean leaflets heavily infested with two spotted adult mites, Tetranyclzus telarius L, within the border of the adhesive preparation on the leaves of the plants under .test. A count of the number of mites transferred were made the same day. The counts ranged from 30* to 300 mites on the six leaves. The plants were kept in the greenhouse -for another fourvdays. A final count of the number of living mites remaining on the leaves was then made. The present control is found by using. the formula:

Final count living mites) Percent, control=100 1 Original count The'control of mites by the chemicals of the present invention at the various concentrations-is shown in the following table (the check treatments without the chemicals had about 20% mortality):

EXAMPLE IV.

This example also illustrates the efiectiveness of the chemicals of the present invention for controlling mites.

Pinto beans in thetwo-leaf stage and grown in 4" baskets under greenhouse conditions at 70 F. F. were used. Two plants for a total of four leaves we-re in each basket for each test. These tests on the chemicals were replicated once.

The untreated leaves were ringed with adhesive and 4050 mites were transferred to each leaf similarly to Example III.

The plants were then sprayed to thoroughly wet the upper surface of the leaves with aqueous solutions of the chemicals at concentrations of p.p.m. and 50* ppm. prepared as in Example III.

The plants were allowed to dry and a count of the mites was made. The plants were kept in the greenhouse for three days. maining on the leaves was then made. The percent control is found by the formula used in Example III.

The control of mites by the chemicals of the present invention is shown in the following table:

' for detailed examples of the same.

Percent Control at- Ohemical 100 ppm. '50 ppm;

Propargyl tridecyl sull'ite 86 '69 Propargyl o-tolyl sulfite;. 59 1-(2-Butyuy1) tridecyl sulfite. 87 58 The chemicals of the present invention may be applied in various manners for the control of insects. They may be applied to loci to be'protected against insects as dusts when admixed with or adsorbed on powdered solid carriers, such as the various mineral silicates, e.g. mica, talc,

pyrophillite and clays, or as liquids or sprays when in a liquid carrier, as in solution in a suitable solvent, such as acetone, benzene or kerosene, or dispersed in a suitable non-solvent medium, for example, water. In protecting plants (the term including plant parts) which are subject to attack by insects, the chemicals of the present invention are preferably applied as aqueous emulsions containing a surface-active dispersing agent, which may be be applied directly to loci to be protected against insects,

or which may be shaken up with water to form a suspension of the chemical (and powdered solid carrier) in water for application in that form. The chemicals of the present invention may be applied to loci to be pro t'ected against insects by the aerosol method. Solutions for the aerosol treatment may be prepared by dissolving the chemical directly in the aerosol carrier which is liquid under pressure but which is a gas at ordinary temperature (e.g. 20 C.) and atmospheric pressure, or the aerosol solution may be prepared by first dissolving the chemical in a less volatile solvent and then admixing such solution with the highly volatile liquid aerosol carrier. The chemii i cals may be used admixed with carriers that are active'of themselves, for example, other insecticides, fungicides or i bactericides. a

A final count of the living mites re- Having thus describeH'mTr invention, what we claim and desire to protect by Letters Patent is:

1. A chemical represented by the general formula in Which R is selected from the group consisting of alkyl having up to 18 carbon atoms, benzyl, cyanoethyl, carbethoxyethy-l, chloroalkyl having up to 5 carbon atoms and up to 3 chloro radicals, phenyl, naphthyl, phenyl and naphthyl having substituents consisting of up to 5 halo radicals selected from the class consisting of lJl'OIllO and chloro, and mono-substituted phenyl and naphthyl having as the substituent an alkyl having up to 9 carbon atoms, and R is acyclic alkynyl of the formula C H in which n is 3 to 10.

2. Propargyl tridecyl sulfite.

I-(Z-butynyl) tridecyl sulfite. 2-(3-butyny1) hexadecyl sulfite. Propargyl o-tolyl sulfite.

References Qited by the Examiner UNITED STATES PATENTS Myles 260-456 Harris et al 260456 X Harris et a1. 260456 X Harris et al. 260-456 Richter 167-30 Brack 260-456 X Dowling 167-30 CHARLES B. PARKER, Primary Examiner.

JULIAN S. LEVITT, Examiner. 

1. A CHEMICAL REPRESENTED BY THE GENERAL FORMULA 